CN1056720A - The direct electrolytic method of granulated metal material - Google Patents
The direct electrolytic method of granulated metal material Download PDFInfo
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- CN1056720A CN1056720A CN 90103824 CN90103824A CN1056720A CN 1056720 A CN1056720 A CN 1056720A CN 90103824 CN90103824 CN 90103824 CN 90103824 A CN90103824 A CN 90103824A CN 1056720 A CN1056720 A CN 1056720A
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Abstract
The invention provides the direct electrolytic method of a kind of granulated metal material, its main points are that the granulated metal material is directly packed in the polyamide fibre cloth bag, in cloth bag, insert conducting plates, place in the foraminous plastics anode superstructure, stainless steel is made negative electrode, put into the electrolyzer that fills electrolytic solution and carry out direct electrolysis, the tin lead metal is deposited on negative electrode and obtains product, the anode sludge after the electrolysis reclaims valuable metal after treatment again, and this method applies to handle the powdery copper ashes of thick tin of tin-smelting plant and lead refinery and refining of lead bullion output especially.
Description
The present invention is a kind of directly from stanniferous, lead, and the direct electrolysis of granulated metal materials such as copper obtains a kind of method of tinsel.The present invention relates to handle all kinds that can produce tinsel in this way and contain tin lead materials, this material has a large amount of stanniferous of thick tin or refining of lead bullion output, plumbous powdery scum silica frost.
The thick tin of tin-smelting plant or lead refinery, the powdery scum silica frost of output is general all more than 10-15% in the refining of lead bullion process, and wherein the copper ashes productive rate reaches 3-5%.For reclaiming the metal in the scum silica frost, each smeltery adopts treatment process inequality both at home and abroad: copper ashes leaches with sulfuric acid behind desulfurization with roasting technique, high tin leached mud of output and copper-bath, high tin leached mud returns the trunk flow process, and copper-bath is used to produce commodity copper sulfate or metallic copper; Copper ashes send fuming furnace to handle; Contain Sn70%, the copper ashes of Cu18% is sent into rotary furnace smelting and is obtained the thick tin of high-copper, separates output with centrifugal filter again and contains Sn60%, and the gunmetal of Cu38% is sold.Domestic tin-smelting plant great majority also adopt the copper ashes desulfurization with roasting technique, and sulfuric acid leaches calcining and produces copper sulfate, and leached mud returns the technology of trunk flow process.This technology exists long flow path, and metal disperses, and the metal direct recovery rate is low, weak points such as production cost height.
The objective of the invention is to avoid above-mentioned the problems of the prior art and provide a kind of the direct electrolysis output of granulated metal material tinsel, tinsel can directly be prepared the high-quality scolder, copper does not return the trunk flow process, reach the raising metal recovery rate, reduce metal loss, reduce production costs, improve the purpose of economical efficiency.
Purpose of the present invention can reach by following measure:
Tin, the various scum silica frost of plumbous pyrorefining output normally make the high impurity of fusing point separate out with compound Solid solution state at low temperatures, and with the liquid metal separation removal.The copper ashes that adds sulphur copper removal output with the tin refining is an example, and the material phase analysis in the slag is: metallic tin accounts for 60-65%, and tin protoxide accounts for 12-17%, and stannous sulfide accounts for 18-25%, and sour insoluble tin accounts for 1.0-2.0%.The tin of metallic state and the tin protoxide that is soluble in acid then account for 70-80%, select a kind ofly can dissolve SnO, can dissolve the solvent of PbO again, as silicofluoric acid solution (H
2SiF
6), will produce following reaction:
Thereby make and be easy to dissolved SnO and PbO enters solution.
The potential property of element from various scum silica frost, tin and plumbous at other impurity elements such as arsenic, copper, antimony, bismuth, in the elements such as iron, the deironing volta potential is all plumbous high than tin, soaks the arsenic of positively charged in the molten process, copper, antimony, impurity elements such as bismuth will be by tin, and electronegative elements such as lead are replaced and are not soaked molten.Wherein more electronegative iron, though current potential is lower than tin lead, but because content is low in the slag, and all exist with compound form, soaking molten amount will be seldom, therefore, copper ashes is after the silicofluoric acid dissolving, gained solution is except that the stanniferous lead ion, and other impurity components will be seldom, is the plumbous bi-metal electrolysis liquid of a kind of ideal tin.
Utilize this electrolytic solution, and above-mentioned slag placed under the electric field action, then can make and wherein do not soaked molten SnO fully, PbO and the tin that exists with metallic state, plumbous at the anode electrochemical solution, by electrolytic solution in cathodic deposition, thereby directly separate with impurity element.
Concrete grammar of the present invention is: the granulated metal scum silica frost of (1) stanniferous lead directly soaks with silicofluoric acid produces electrolytic solution.Silicofluoric acid concentration 200-250g/l soaks liquid-solid ratio 1: 0.5-1.0, can reach in the solution to contain Sn after directly soaking
++30-60g/l, Pb
++10-15g/l contains free H
2SiF
6120-200g/l has reached the standard of electrolytic solution fully.
(2) the direct electrolysis of anode is done in the pack of granulated metal material.The granulated metal material is directly packed in the bright and beautiful human relations cloth bag, in cloth bag, insert conducting plates graphite or contain tin and plumbous crude metal, and place in the foraminous plastics anode superstructure, stainless steel is made negative electrode, put into the electrolyzer that fills electrolytic solution and carry out direct electrolysis, tin lead metal electrolytic deposition obtains product at negative electrode, and product is except that main metal, and other impurity component content all can reach the standard of spy's tin.
(3) the electrolysis residue is earlier with the washing of minor amount of silicon fluoric acid, and with the less water washing, washing lotion contains Sn again
++Directly return electrolyzer about 30g/l and do the electrolytic solution use, keep the balance of electrolytic solution.
(4) electrolysis technology condition.Bath composition Sn
++30-60g/l, Pb
++10-50g/l, free H
2SiF
6120-200g/l, electrolytic solution adds additive gelatin and Beta Naphthol 99MIN.Current density 70-200A/m
2, bath voltage 0.5-4.0V, normal temperature electrolysis.
(5) ANODE SLIME TREATMENT.The anode sludge of output is with a spot of silicofluoric acid and water washing after direct electrolysis, and wash water returns to be separated liquid and use, and the anode sludge is through processing recovery valuable metal again.
The present invention compared with prior art has following advantage:
(1) adopts granulated metal material direct electrolysis method, avoided the pyrometallurgical smelting of common employing, directly obtain product, saved the energy, improved labor condition.
(2) the granulated metal material adopts fluosilicic to soak as electrolytic solution, has avoided electric molten liquid making process, has simplified technology.
(3) be convenient to the comprehensive recovery of impurity element, directly the melting impurity element circulates on stream, adopts the direct electrolysis method impurity element to be enriched in the anode sludge, can comprehensively reclaim elements such as copper, arsenic from the anode sludge, the rate of recovery of raising valuable metal.
(4) direct electrolysis method bath voltage allowed band is wide, operation easily, and bath voltage is controlled in the 0.5-4V scope, and negative electrode can obtain qualified product equally.
Embodiment:
The present invention is described in further detail below in conjunction with (accompanying drawing) embodiment.
Utilize the present invention to handle Yunnan Tin Industrial Corp.'s the first, three smeltery's tin refinement and remove copper ashes.
One, material properties
Copper ashes bulk density 2.99t/m
3
1. sreen analysis
| Grade (mm) | +2.5 | 0.9 | 0.35 | 0.15 | 0.1 | -0.1 |
| % | 17.68 | 16.48 | 22.39 | 22.29 | 4.4 | 16.76 |
2. copper ashes and assorted scruff chemical composition analysis
| Composition % | Sn | Pb | Cu | As | Sb | S | Fe | Bi |
| One smelting copper ashes, the three smelting copper ashes scruff of mixing | 60.26 42.21 71.31 | 8.15 28.00 12.12 | 12.32 18.02 4.69 | 2.22 0.225 0.025 | 0.095 0.25 0.025 | 7.24 0.98 .0007 | 0.39 0.3 .073 | 0.14 0.05 0.14 |
The bath composition that copper ashes directly soaks generation is
| Form | Sn | Sn ++ | Pb ++ | Sb | Cu | Fe | Free H 2SiF 6 |
| g/l | 37.82 | 35.84 | 15.93 | 〈0.01 | 0.01 | 0.07 | 147.61 |
Three, electrolysis control condition
Current density: 70-80A/m
2
Electrolysis temperature: normal temperature
Circulation of elecrolyte amount: 10-15l/min
Every groove anode copper ashes is heavy: 334.17 kilograms
Negative electrode: 3.19m
2/ groove
Additive: gelatin, Beta Naphthol 99MIN
Bath voltage: 0.48-2,4V
Four, the negative electrode product composition
| Element % | Sn | Pb | Cu | Sb | As | Bi | Fe | Sn+Pb |
| 1 | 59.63 | 40.03 | 〈.0011 | .0005 | .00006 | .0042 | .0015 | 99.66 |
| 2 | 58.87 | 40.76 | 〈.001 | .0004 | .00011 | .0022 | .0012 | 99.63 |
Four, main economic and technical indices
| Direct power consumption degree/t product | Acid consumption Kg/t product | Water consumption t/t product | Current efficiency % | Direct yield % | Total yield % | ||
| Sn | Pb | Sn | Pb | ||||
| 1043 | 57.52 | 0.61 | 97.99 | 62.1 | 75.3 | 96.13 | 95.11 |
Five, anode sludge composition
| Element | Sn | Pb | Cu | As | Sb | Bi | Fe | S |
| % | 33.80 | 12.24 | 26.38 | 1.12 | 0.44 | 0.17 | 0.1 | 12.88 |
The anode sludge carries out oxidizing roasting at 750-800 ℃, and fired slags leaches with sulfuric acid, leaches liquid-solid ratio 4: 1,80 ℃ of 30 minutes times of temperature.Leach liquor crystallisation by cooling output commodity copper sulfate, copper sulfate crystal composition: contain CuSO
45H
2O＞99%, water-insoluble＜0.02%, free H
2SO
4＜0.1-0.2%.Reach country-level product standard (GB437-80).The sulfuric acid leached mud contains Sn48-51%, and Cu0.2-0.3% returns tin and smelts the trunk flow process.
Claims (6)
1, a kind of tin that contains at least, plumbous, granulated metal materials such as copper carry out the method for direct electrolytic recovery valuable metal, it is characterized in that the granulated metal material packs in the bright and beautiful human relations cloth bag, in bag, insert electrical conductor, place in the foraminous plastics anode superstructure, stainless steel is made negative electrode, puts into the electrolyzer that fills electrolytic solution and carries out direct electrolysis, tin lead metal electrolytic deposition obtains product at negative electrode, and the anode sludge reclaims valuable metal after treatment.
2, method according to claim 1 is characterized in that electrolytic solution is silicofluoric acid electrolytic solution, is to adopt granulated metal material silicofluoric acid to soak to obtain.
3, method according to claim 2 is characterized in that the composition of electrolytic solution is: contain free H
2SiF
6120-200g/l, Sn
++30-60g/l, Pb
++10-50g/l.
4, method according to claim 1 is characterized in that direct electrolytic technical qualification are: bath voltage 0.5-4.0V, current density 70-200A/m
2, the normal temperature electrolysis.
5, method according to claim 1 is characterized in that inserting in the metal pulverulent material, and the conductor in the bright and beautiful human relations cloth bag of packing into is graphite or contains tin and plumbous crude metal.
6, method according to claim 1 is characterized in that the anode sludge of direct electrolysis output, returns to make electrolytic solution and use the treated again recovery valuable metal of the anode sludge after washing after minor amount of silicon fluoric acid and water washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90103824 CN1056720A (en) | 1990-05-19 | 1990-05-19 | The direct electrolytic method of granulated metal material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90103824 CN1056720A (en) | 1990-05-19 | 1990-05-19 | The direct electrolytic method of granulated metal material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1056720A true CN1056720A (en) | 1991-12-04 |
Family
ID=4878256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90103824 Pending CN1056720A (en) | 1990-05-19 | 1990-05-19 | The direct electrolytic method of granulated metal material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1056720A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942675A (en) * | 2010-09-10 | 2011-01-12 | 常州大学 | Method for recycling Sn<2+> in waste water by electrolytic reduction |
| CN102424983A (en) * | 2011-12-28 | 2012-04-25 | 个旧市富祥工贸有限责任公司 | Combined electrolysis process for high-impurity lead-tin alloy |
| CN102618883A (en) * | 2012-02-13 | 2012-08-01 | 北京化工大学 | Method for direct electrolytic refining of crude lead |
| CN102677094A (en) * | 2011-11-15 | 2012-09-19 | 王应龙 | Copper and tin plated iron needle recovery device and copper and tin plated iron needle recovery method |
| CN102978657A (en) * | 2012-12-07 | 2013-03-20 | 来宾华锡冶炼有限公司 | Method for separating antimony from tin-antimony alloy |
| CN103374728A (en) * | 2012-04-12 | 2013-10-30 | 梁达保 | Method for preparing lead electrolyte by utilizing industrial waste liquids |
| CN103510109A (en) * | 2013-10-24 | 2014-01-15 | 北京化工大学 | Method for recycling lead-containing grid of waste lead-acid battery through self-gravity contact electrolysis |
| CN105018963A (en) * | 2014-04-21 | 2015-11-04 | 上海奇谋能源技术开发有限公司 | Method for performing direct electrorefining on metal crushed aggregates |
| CN110050089A (en) * | 2016-12-19 | 2019-07-23 | 威立雅环境公司 | For extract include tin and/or lead in conductive mixture electrolytic method |
| CN110219019A (en) * | 2019-07-22 | 2019-09-10 | 广东汉合有色金属有限公司 | A kind of diaphragm electrolysis technique of tin copper ashes |
| CN112064062A (en) * | 2020-11-10 | 2020-12-11 | 矿冶科技集团有限公司 | Method for preparing crude lead by waste lead plaster without pre-desulfurization combined electrolysis |
-
1990
- 1990-05-19 CN CN 90103824 patent/CN1056720A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942675A (en) * | 2010-09-10 | 2011-01-12 | 常州大学 | Method for recycling Sn<2+> in waste water by electrolytic reduction |
| CN102677094A (en) * | 2011-11-15 | 2012-09-19 | 王应龙 | Copper and tin plated iron needle recovery device and copper and tin plated iron needle recovery method |
| CN102677094B (en) * | 2011-11-15 | 2014-08-13 | 王应龙 | Copper and tin plated iron needle recovery device and copper and tin plated iron needle recovery method |
| CN102424983A (en) * | 2011-12-28 | 2012-04-25 | 个旧市富祥工贸有限责任公司 | Combined electrolysis process for high-impurity lead-tin alloy |
| CN102618883B (en) * | 2012-02-13 | 2014-12-03 | 北京化工大学 | Method for direct electrolytic refining of crude lead |
| CN102618883A (en) * | 2012-02-13 | 2012-08-01 | 北京化工大学 | Method for direct electrolytic refining of crude lead |
| CN103374728A (en) * | 2012-04-12 | 2013-10-30 | 梁达保 | Method for preparing lead electrolyte by utilizing industrial waste liquids |
| CN103374728B (en) * | 2012-04-12 | 2016-08-03 | 梁达保 | Utilize the method that industrial wastes produces lead electrolytic solution |
| CN102978657A (en) * | 2012-12-07 | 2013-03-20 | 来宾华锡冶炼有限公司 | Method for separating antimony from tin-antimony alloy |
| CN103510109B (en) * | 2013-10-24 | 2016-03-02 | 北京化工大学 | The method of the leaded grid of waste lead acid battery is reclaimed from gravity contact electricity solution |
| CN103510109A (en) * | 2013-10-24 | 2014-01-15 | 北京化工大学 | Method for recycling lead-containing grid of waste lead-acid battery through self-gravity contact electrolysis |
| CN105018963A (en) * | 2014-04-21 | 2015-11-04 | 上海奇谋能源技术开发有限公司 | Method for performing direct electrorefining on metal crushed aggregates |
| CN110050089A (en) * | 2016-12-19 | 2019-07-23 | 威立雅环境公司 | For extract include tin and/or lead in conductive mixture electrolytic method |
| CN110050089B (en) * | 2016-12-19 | 2021-06-25 | 威立雅环境公司 | Electrolytic process for extracting tin and/or lead contained in an electrically conductive mixture |
| US11280011B2 (en) | 2016-12-19 | 2022-03-22 | Veolia Environment VE | Electrolytic method for extracting tin and/or lead contained in an electrically conductive mixture |
| CN110219019A (en) * | 2019-07-22 | 2019-09-10 | 广东汉合有色金属有限公司 | A kind of diaphragm electrolysis technique of tin copper ashes |
| CN112064062A (en) * | 2020-11-10 | 2020-12-11 | 矿冶科技集团有限公司 | Method for preparing crude lead by waste lead plaster without pre-desulfurization combined electrolysis |
| CN112064062B (en) * | 2020-11-10 | 2021-02-12 | 矿冶科技集团有限公司 | Method for preparing crude lead by waste lead plaster without pre-desulfurization combined electrolysis |
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